KR20090043543A - Insecticidal n-substituted (heteroaryl)alkyl sulfilimines - Google Patents

Abstract

The N-substituted (heteroaryl) alkyl sulfylimines according to the invention are effective in controlling insects.

N-substituted (heteroaryl) alkyl sulphlimines, insect control

Description

Insecticidal N-substituted (heteroaryl) alkyl sulfilimines {INSECTICIDAL N-SUBSTITUTED (HETEROARYL) ALKYL SULFILIMINES}

This application claims the benefit of US Provisional Application No. 60 / 841,934, filed September 1, 2006.

The present invention relates to the use of novel N-substituted (heteroaryl) alkyl sulfimines and their insects, in particular aphids and other sucking insects, as well as certain other invertebrates. The present invention also encompasses novel synthetic procedures for the preparation of the compounds, pesticide compositions containing the compounds and insect control methods using the compounds.

New pesticides are urgently needed. Insects are developing resistance to pesticides currently used. More than 400 arthropods are resistant to one or more pesticides. The expression of resistance to some conventional pesticides such as DDT, carbamate and organophosphate is well known. However, resistance is expressed even for some of the newer pyrethroid pesticides. Thus, there is a need for new pesticides, especially compounds with new or atypical modes of action.

The present invention relates to compounds useful for controlling insects, in particular for controlling aphids and other sucker insects. More specifically, the present invention relates to compounds of formula (I)

Where

Het is represented by the formula

Represents;

X is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ alkoxy , C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ⁶ where m is an integer from 0 to 2, COOR ⁴ or CONR ⁴ R ⁵ ;

Y is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ¹ , wherein m is an integer from 0 to 2, COOR ⁴ , CONR ⁴ R ⁵ , aryl or heteroaryl;

Z is C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ¹ (where m is an integer from 0 to 2), COOR ⁴ or CONR ⁴ R ⁵ ;

n is an integer from 0 to 3;

L represents a single bond, —CH ₂ — or —CH (CH ₂ ) _p −, where p is an integer from 1 to 3, wherein R ¹ , S and L or R ² , L and the co-carbon to which they are attached Together represent a 4, 5 or 6 membered ring having up to 1 heteroatom;

R ¹ represents C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ haloalkenyl, arylalkyl, heteroarylalkyl Or together with L or R ² form a 4, 5 or 6 membered saturated ring;

R ² and R ³ are independently hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloal Kenyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, CN, SO _m R ⁶ , wherein m is an integer from 0 to 2, COOR ⁴ , CONR ⁴ R ⁵ , arylalkyl, heteroarylalkyl Or R ² and R ³ and the co-carbon to which they are attached form a 3 to 6 membered ring, or R ² and R ¹ together form a 4, 5 or 6 membered saturated ring;

R ⁴ and R ⁵ are independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ haloalkenyl, Aryl, heteroaryl, arylalkyl or heteroarylalkyl;

R ⁶ represents C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ haloalkenyl, arylalkyl, heteroarylalkyl Represent;

Q represents NO ₂ or CN.

Preferred compounds of formula I include the following classes:

(1) A compound of formula (I) wherein Het is (6-substituted) pyridin-3-yl or (2-substituted) thiazol-5-yl, Z is C ₁ -C ₂ haloalkyl and Y is hydrogen ;

(2) A compound of formula (I) having the formula wherein R ² and R ³ are as defined above, R ¹ is methyl, n is 1 and L is a single bond

;

;

(3) n is 1, R ¹ , S and L together form a 4, 5 or 6 membered saturated ring, L is -CH (CH ₂ ) _p -and R ¹ is -CH _2- Compound of formula I with structural formula

;

;

(4) n is 0, R ¹ , S and L together form a 4, 5 or 6 membered standard ring, L is -CH (CH ₂ ) _p -and R ¹ is -CH _2- Compound of formula I with structural formula

;

;

(5) A compound of formula I wherein Q is CN.

Those skilled in the art will appreciate that most preferred compounds are generally compounds composed of combinations of the above preferred classes.

The present invention also provides novel processes for the preparation of compounds of formula (I), as well as novel compositions and methods of use, which will be described in detail below.

In this specification, all temperatures are given in degrees Celsius unless stated otherwise and all percentages are by weight.

The terms "alkyl", "alkenyl" and "alkynyl" as used herein, as well as "alkoxy", "acyl", "alkylthio", "arylalkyl", "heteroarylalkyl" and "alkylsulfonyl" Derivative terms such as include straight, branched and cyclic moieties within their scope. Thus, typical alkyl groups include methyl, ethyl, 1-methyl-ethyl, propyl, 1,1-dimethylethyl and cyclopropyl. Unless stated otherwise specifically, each is unsubstituted or selected from, but not limited to, halogen, hydroxy, alkoxy, alkylthio, C ₁ -C ₆ acyl, formyl, cyano, aryloxy or aryl Substituents may be substituted with one or more substituents provided that they are stereocompatible and meet the rules of chemical bonding and strain energy. The terms "haloalkyl" and "haloalkenyl" include alkyl and alkenyl groups substituted with 1 to the maximum possible number of halogen atoms (all combinations of halogens are included). The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine, with fluorine being preferred. The terms "alkenyl" and "alkynyl" are intended to include one or more unsaturated bonds.

The term "aryl" means a phenyl, indanyl or naphthyl group. The term “heteroaryl” means a 5 or 6 membered aromatic ring containing one or more heteroatoms, ie N, O or S, which heteroaromatic rings may be conjugated with other aromatic systems. Aryl or heteroaryl substituents are unsubstituted or halogen, hydroxy, nitro, cyano, aryloxy, formyl, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxy, C ₁ -C ₆ acyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, aryl, C ₁ -C ₆ OC (O) alkyl, C ₁ -C ₆ NHC (O) alkyl, C (O) OH, C ₁ -C ₆ C (O) Oalkyl, C May be substituted with one or more substituents selected from (O) NH ₂ , C ₁ -C ₆ C (O) NHalkyl, or C ₁ -C ₆ C (O) N (alkyl) ₂ , provided that the substituents are stereocompatible Properties and satisfies the rules of chemical bonding and strain energy.

The compounds of the present invention may exist as one or more stereoisomers. Various stereoisomers include geometric isomers, diastereomers and enantiomers. Thus, the compounds of the present invention include racemic mixtures, individual stereoisomers and optically active mixtures. Those skilled in the art will appreciate that one stereoisomer may be more active than another. Individual stereoisomers and optically active mixtures can be obtained by selective synthesis procedures, conventional synthesis procedures using degraded starting materials, or conventional degradation procedures.

Compounds of formula (I) wherein Q is NO ₂ and R ¹ , R ² , R ³ , n and L are as defined above can be prepared by the method illustrated in Scheme A below.

In step a of Scheme A, the sulfide of formula A is reacted with nitramide in the presence of acetic anhydride to give sulfilimine (I) (Shitov, OP; Seleznev, A. P; Tartakovski, VA Inst. Org Kim.im.Zelinskogo, Moscow, USSR.Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1991), (5), 1237-8.]).

Compounds of formula (Ia) wherein Q is CN and Het, R ¹ , R ² , R ³ , n and L are as defined above can be prepared by the method illustrated in Scheme B below. Thus, the precursor sulfide is oxidized with iodobenzene diacetate at 0 ° C. in the presence of cyanamide to give sulfilimine (Ia). The reaction can be carried out in a polar aprotic solvent such as CH ₂ Cl ₂ .

Precursor sulfides (A) can in turn be prepared in different ways as illustrated in the following schemes C, D, E, F and G.

In Scheme C, sulfides of Formula A ₁ wherein L is a single bond, n is 1, R ³ = H, and R ¹ , R ² and Het are as defined above, It can be prepared from a halide of formula D by nuclear substitution.

In Scheme D, sulfides of Formula A ₂ in which L is a single bond, n is 3, R ³ = H, and R ¹ , R ² and Het are as defined above, are selected from potassium tert- Reaction with 2-mono-substituted methyl malonate in the presence of a base such as butoxide to give a 2,2-disubstituted malonate, hydrolysis under basic conditions to form diacids, the diacids by heating Cyclization yields monoacid, the monoacid is reduced with borane-tetrahydrofuran complex to yield an alcohol, and the alcohol is tosylated with toluenesulfonyl chloride (tosyl chloride) in the presence of a base such as pyridine. Can be prepared by replacing the tosylate with the sodium salt of the thiol of interest.

In Scheme E, sulfides of Formula A ₃ in which L is a single bond, n is 2, R ³ = H, and R ¹ , R ² and Het are as defined above, use a strong base from the nitrile of Formula F Deprotonation and alkylation with alkyl iodide to afford α-alkylated nitriles and hydrolysis of the α-alkylated nitriles in the presence of a strong acid such as HCl to yield an acid, the acid being borane- Reduction with tetrahydrofuran complex yields an alcohol, the alcohol is tosylated with tosyl chloride in the presence of a base such as pyridine to give tosylate, replacing the tosylate with the sodium salt of the desired thiol It can manufacture by making it.

In Scheme F, n is 0, R ¹ is -CH _2- , L is -CH (CH ₂ ) _p- , where p is 2 or 3, and R ¹ , S and L together are 5 or Sulphides of formula A ₄ , which form a six-membered ring and Het is defined above, can be prepared from tetrahydrothiophene (p = 2) or pentamethylene sulfide (p = 3) (G). The cyclic sulfide starting material is chlorinated with N-chlorosuccinimide in benzene and then alkylated with a specific lithiated heterocycle or Grignard reagent to meet the desired sulfide (A ₄ ). It can be produced in a yield yield.

More effective protocols for obtaining cyclic sulfides of formula A ₄ are illustrated in Scheme G below, wherein Het is 6-substituted pyridin-3-yl and Z is as defined above. Thus, thiourea is added to the substituted chloromethyl pyridine and, after hydrolysis, alkylated under aqueous basic conditions with the appropriate bromo chloroalkane (p = 1, 2 or 3) to give sulfide (H). Subsequent cyclization of compound H in the presence of a base such as potassium t-butoxide in a polar aprotic solvent such as THF affords cyclic sulfide (A ₄ ).

Certain sulfides of Formula A ₁ wherein Het is substituted pyridin-3-yl, Z is as defined above, and R ¹ , R ² = CH ₃ can be prepared separately by the method illustrated in Scheme H below. have. Thus, the appropriate enone is coupled with dimethylaminoacrylonitrile and cyclized with ammonium acetate in DMF to give the corresponding 6-substituted nicotinonitrile. Treatment with methyl-magnesium bromide, reduction with sodium borohydride, chlorination with thionyl chloride and nucleophilic substitution with the sodium salt of alkyl thiols give the desired sulfide (A ₁ ).

A variation of Scheme H is illustrated in Scheme I, wherein an enamine formed from the addition of an amine, for example pyrrolidine, with Michael adducts of α, β-unsaturated aldehydes appropriately substituted with certain sulfides Coupling with a substituted enon and cyclization with ammonium acetate in CH ₃ CN affords the desired sulfide (A ₁ ) in which R ¹ , R ² , R ³ and Z are as defined above.

Cyclic pyridyl sulfide (A ₅ ) in which n = 1, L =-(CH ₂ )-and R ¹ , R ² are linked to form a 5-membered ring using a variant of the method illustrated in Scheme J. Can be prepared. Thus, the reaction of tetrahydrothiophen-3-one with triphenylphosphine and dimethyl-carbonate gives the corresponding olefins, and then hydroformylated with hydrogen and carbon monoxide in the presence of a rhodium catalyst at elevated temperature to form aldehyde (N ). The remaining steps for converting aldehyde to sulfide (A ₅ ) follow the same protocol as described in Scheme I above.

The same meanings as in Reaction Scheme K is R ¹ and Z defined above, n = 1 a, L, R ² and co carbon with which they are connected. 4, 5, or 6 membered ring (x = 0 to 2) the formula A ₆ to form a The sulfide of was added to a cyclic ketone such as cyclopentanone (x = 1) after halogen metal exchange with isopropyl Grignard or n-butyl lithium from 2-substituted 5-bromo-pyridine and acidic conditions Dehydrogenated to olefin, boron hydride (borane in tetrahydrofuran), oxidative decomposition (sodium hydroxide and hydrogen peroxide), and the resulting alcohol (treated with methanesulfonyl chloride and triethyl amine) with methanesulfonyl groups And can be prepared by nucleophilic substitution with sodium salts of alkyl thiols.

Example I. Preparation of {1- [6- (trifluoromethyl) pyridin-3-yl] methyl} -λ ⁴ -sulfanylidenecyanamide (1)

To a solution of 3-chloromethyl-6- (trifluoromethyl) pyridine (5.1 g, 26 mmol) in dimethyl sulfoxide (DMSO; 20 mL) was added sodium thiomethoxide (1.8 g, 26 mmol) in one portion. . A vigorous exothermic reaction was observed and the reaction thickened. The reaction was stirred for 1 hour, then additional sodium thiomethoxide (0.91 g, 13 mmol) was added slowly. The reaction was stirred overnight and then poured into H ₂ O and several drops of concentrated HCl were added. The mixture was extracted with Et ₂ O (3 × 50 mL) and the organic layers combined, washed with brine, dried over MgSO ₄ , filtered and concentrated. The crude product was purified by chromatography (Prep 500, 10% acetone / hexane, v / v) to give sulfide (A) (3.6 g, 67%) as pale yellow oil.

To a solution of sulfide (A) (3.5 g, 17 mmol) and cyanamide (1.4 mg, 34 mmol) in CH ₂ Cl ₂ (30 mL) at 0 ° C. was added iodobenzenediacetate (11.0 g, 34 mmol). It was added all at once. The reaction was stirred for 30 minutes and then allowed to come to room temperature overnight. The mixture was diluted with CH ₂ Cl ₂ (50 mL) and washed with H ₂ O. The aqueous layer was extracted with ethyl acetate (4 x 50 mL) and the combined CH ₂ Cl ₂ and ethyl acetate layers were dried over MgSO ₄ and concentrated. The crude product was triturated with hexane and purified by chromatography (chromatotron, 60% acetone / hexane, v / v) to give sulfilimine (1) (0.60 g, 14%) as a yellow gum. IR (film) 3008, 2924, 2143, 1693 cm ⁻¹ ;

Example II. Preparation of (1- {6- [chloro (difluoro) methyl] pyridin-3-yl} ethyl) (methyl) -λ ⁴ -sulfanylidenecyamide (2)

(3E) -1-Chloro-4-ethoxy-1,1-difluorobut-3-en-2-one (7.36 g, 40 mmol) is dissolved in anhydrous toluene (40 mL) and 3 at room temperature Treated with -dimethylaminoacrylonitrile (4.61 g, 48 mmol). The solution was heated at 100 ° C. for 3.5 h. The solvent is then removed under reduced pressure and the remaining mixture is redissolved in dimethyl formamide (DMF; 20 mL), treated with ammonium acetate (4.62 g, 60 mmol) and stirred at rt overnight. Water was added to the reaction mixture and the resulting mixture was extracted twice with ether-CH ₂ CH ₂ (1: 2, v / v). The combined organic layers were washed with brine, dried, filtered and concentrated. The residue was purified on silica gel to give 3.1 g of 6- [chloro (difluoro) methyl] nicotinonitrile (A) as light oil in 41% yield. GC-MS: mass calcd. For C ₇ H ₃ ClF ₂ N ₂ [M] ⁺ 188. found 188.

6- [Chloro (difluoro) methyl] nicotinonitrile (A) (3.0 g, 15.8 mmol) was dissolved in anhydrous ether (25 mL) and cooled in an ice water bath. A 3 M solution of methylmagnesium bromide (6.4 mL, 19 mmol) in hexanes was added via syringe. After the addition was completed, the mixture was stirred at 0 ° C. for 5 hours and then at room temperature for 10 hours. The reaction was slowly quenched with 1 N aqueous citric acid solution at 0 ° C. and the resulting mixture was stirred at rt for 1 h. The pH was adjusted back to 7 with saturated aqueous NaHCO ₃ solution. The two phases were separated and the aqueous phase was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated. The remaining mixture was purified on silica gel eluting with 15% acetone (v / v) in hexane to give the desired product 1- {6- [chloro (difluoro) methyl] pyridin-3-yl} ethanone as a brownish oil. (B) 0.88 g was obtained in 30% yield. GC-MS: mass calcd. For C ₈ H ₆ ClF ₂ NO [M] ⁺ 205. found 205.

To a solution of 1- {6- [chloro (difluoro) methyl] pyridin-3-yl} ethanone (B) (0.85 g, 4.14 mmol) in MeOH (10 mL) at 0 ° C., NaBH ₄ (0.16 g, 4.14 mmol) was added. The mixture was stirred for 30 minutes and 2 M HCl aqueous solution was added until pH 7 was reached. The solvent was removed under reduced pressure and the remaining mixture was extracted with CH ₂ Cl ₂ (2 × 50 mL). The combined organic layers were dried over anhydrous Na ₂ S0 ₄ , filtered, concentrated and dried in vacuo to analytically pure 1- {6- [chloro (difluoro) methyl] -pyridin-3-yl} on GC-MS. 0.798 g of ethanol (C) were obtained as a pale yellow oil in 93% yield. GC-MS: mass calcd. For C ₈ H ₆ ClF ₂ NO [M] ⁺ 207. found 207.

Thionyl chloride (0.54 mL, 7.54 mmol) in a solution of 1- {6- [chloro (difluoro) methyl] pyridin-3-yl} ethanol (0.78 g, 3.77 mmol) in CH ₂ Cl ₂ (40 mL). Was added dropwise at room temperature. After 1 hour, the reaction was slowly quenched with saturated aqueous NaHCO ₃ solution and the two phases were separated. The organic layer was dried over Na ₂ S0 ₄ , filtered, concentrated and dried in vacuo to give 0.83 g of crude 2- [chloro (difluoro) methyl] -5- (1-chloroethyl) pyridine (D) as a brown oil. Was obtained in 98% yield and used directly in the next step reaction. GC-MS: mass calcd. For C ₈ H ₇ Cl ₂ F ₂ N [M] ⁺ 225. found 225.

Sodium thiomethoxide (0.52 g, 7.4) in a solution of 2- [chloro (difluoro) methyl] -5- (1-chloroethyl) pyridine (D) (0.81 g, 3.6 mmol) in ethanol (10 mL) mmol) was added all at once with stirring at 0 ° C. After 10 minutes, the mixture was allowed to come to room temperature and stirred overnight. The solvent ethanol was then removed under reduced pressure and the residue was taken up again in ether / CH ₂ Cl ₂ and brine. The two phases were separated and the aqueous layer was extracted once more with CH ₂ Cl ₂ . The combined organic layers were dried over anhydrous Na ₂ SO ₄ , filtered, concentrated and purified on silica gel with 5% ethyl acetate (v / v) in hexanes to give 2- [chloro (difluoro) methyl] -5- 0.348 g of [1- (methylthio) ethyl] pyridine (E) was obtained in 40% yield. GC-MS: mass calcd. For C ₉ H ₁₀ ClF ₂ NS [M] ⁺ 237. found 237.

2- [chloro (difluoro) methyl] -5- [1- (methylthio) ethyl] pyridine (E) (0.32 g, 1.35 mmol) and cyanamide (0.058 g) in tetrahydrofuran (THF; 7 mL) , 1.35 mmol) was added iodobenzene diacetate (0.44 g, 1.35 mmol) in one portion at 0 ° C. and the resulting mixture was stirred at this temperature for 1 hour and then at room temperature for 2 hours. The solvent is removed under reduced pressure and the resulting mixture is dissolved in CH ₂ Cl ₂ , washed with semi-saturated brine, dried over anhydrous Na ₂ SO ₄ , filtered, concentrated and 50% acetone in hexane (v / Purified on silica gel using v) (1- {6- [chloro- (difluoro) methyl] pyridin-3-yl} ethyl) (methyl) -λ ⁴ -sulfanylidenecyamide ( 2) 0.175 g was obtained in 48% yield.

Example III. Preparation of {1- [6- (trichloromethyl) pyridin-3-yl] ethyl} (methyl) -λ ⁴ -sulfanylidenecyamide (3)

A mixture of 5-ethylpyridine-2-carboxylic acid (1.98 g, 13 mmol), phenylphosphonic acid dichloride (2.8 g, 14.3 mmol) and phosphorus pentachloride (7.7 g, 32 mmol) was stirred and heated slowly. When a clear yellow liquid formed, the mixture was heated to reflux overnight. After cooling, the volatiles were removed under reduced pressure. The residue was carefully poured into a saturated aqueous sodium carbonate solution in an ice-water bath. The aqueous phase was then extracted twice with CH ₂ Cl ₂ . The combined organic layers were washed with brine, dried over anhydrous Na ₂ SO ₄ , filtered, concentrated and partially purified on silica gel eluted with 10% EtOAc (v / v) in hexanes to 5-ethyl-2- (trichloro). 2.7 g of crude product were obtained, containing both rhomethyl) pyridine and 5- (1-chloroethyl) -2- (trichloromethyl) pyridine in a ratio of approximately 3: 1 (GC data, C ₈ H ₈ Cl ₃ N And mass calcd. [M] for C ₈ H ₇ Cl ₄ N ⁺ 223 and 257 respectively. Found 223 and 257, respectively.

A mixture of the abovementioned crude product (2.6 g) in carbon tetrachloride (100 mL) was treated with about 80% N-bromosuccinimide (1.9 g, 11 mmol) and benzoylperoxide (0.66 g, 0.275 mmol) , Refluxed overnight. The solid was filtered off, the filtrate was concentrated and the resulting residue was purified on silica gel using 4% EtOAc (v / v) in hexanes to afford the desired product 5- (1-bromoethyl) -2- as a yellow solid. 1.0 g of (trichloromethyl) pyridine (A) was obtained. The combined yield for both steps was 25%. GC-MS: mass calcd. For C ₈ H ₇ BrCl ₃ N [M-1-Cl] ⁺ 266. found 266.

A solution of 5- (1-bromoethyl) -2- (trichloromethyl) pyridine (A) (0.95 g, 3.14 mmol) in ethanol (15 mL) was added sodium thiomethoxide (0.44 g, 6.29) at 0 ° C. mmol). The mixture was stirred at rt overnight. The solvent ethanol was then removed under reduced pressure and the residue was taken up again in CH ₂ Cl ₂ and brine. The two phases were separated and the organic layer was dried over anhydrous Na ₂ SO ₄ , filtered and concentrated. The residue was purified on silica gel using 5% EtOAc (v / v) in hexanes to give 0.57 g of partially pure 5- [1- (methylthio) ethyl] -2- (trichloromethyl) pyridine (B) 67 Obtained in% crude yield. GC-MS: mass calcd. For C ₉ H ₁₀ Cl ₃ NS [M] ⁺ 269. found 269.

5- [1- (methylthio) ethyl] -2- (trichloromethyl) pyridine (B) (0.55 g, 2.3 mmol) and cyanamide (0.097 g, 2.3 mmol) in THF (7 mL) cooled to 0 ° C. To the stirred solution of iodobenzene diacetate (0.75 g, 2.3 mmol) was added in one portion. The resulting mixture was stirred at 0 ° C. for 1 hour and then at room temperature for 2 hours. The solvent was removed in vacuo and the resulting mixture was purified on silica gel using 50% acetone (v / v) in hexanes to afford {1- [6- (trichloromethyl) pyridin-3-yl] ethyl} as off-white solid. 0.254 g of (methyl) -λ ⁴ -sulfanylidenecyanamide (3) was obtained in 40% yield.

Example IV. Preparation of (1E)-[1- (2-chloropyrimidin-5-yl) ethyl] (methyl) -λ ⁴ -sulfanylidenecyamide (4)

A solution of 2-chloro-5-ethylpyrimidine (1.15 g, 8.1 mmol) in 20 mL of carbon tetrachloride was treated with N-bromosuccinimide (1.50 g, 8.4 mmol) and a catalytic amount of benzoyl peroxide and the mixture was 75 Heated to ° C. After several hours and catalyst addition the starting material was consumed completely. The solid was removed and the filtrate was concentrated under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel using a mixture of ethyl acetate and petroleum ether as elution solvent. The solvent was removed under reduced pressure to give 0.64 g (36%) of 5- (1-bromoethyl) -2-chloropyrimidine (A) as a clear liquid: ¹ H NMR (CDCl ₃ ) δ 8.70 (s, 2H ), 5.15 (q, J = 8.0 Hz, 1H), 2.10 (d, J = 8.0 Hz, 3H); GCMS (FID) m / z 222 (M ⁺ ). In addition, 0.44 g (18%) of some corresponding dibromo compound was isolated as a white solid: mp 84-85 ° C .; ¹ H NMR (CDCl ₃ ) d 9.00 (s, 2H), 3.00 (s, 3H); LCMS (ESI) m / z 298 (M + H).

2-Chloro-5- [1- (methylthio) ethyl] pyrimidine (B) was obtained as a pale yellow syrup from bromide (A) using the same procedure described in Example III (B) above. ¹ H NMR (CDCl ₃ ) δ 8.60 (s, 2H), 3.85 (q, J = 8.0 Hz, 1H), 1.98 (s, 3H), 1.65 (d, J = 8.0 Hz, 3H); GCMS (FID) m / z 188 (M ⁺ ).

Title compound (1E)-[1- (2-chloropyrimidin-5-yl) ethyl] (methyl) -λ ⁴ -sulfa from sulfide (B) using the same procedure described in Example III (C) above Nilidenecyanamide (4) was obtained as a 2: 1 mixture of pale orange syrup and diastereomers.

Example V. Preparation of (1E) -methyl {[2- (trifluoromethyl) -1,3-thiazol-5-yl] methyl} -λ ⁴ -sulfanylidenecyamide (5)

5-[(methyl) from 5- (bromomethyl) -2- (trifluoromethyl) -1,3-thiazole (A) [USP 5,338,856] using the same procedure described in Example III (B) above. Thio) methyl] -2- (trifluoromethyl) -1,3-thiazole (B) was obtained as pale orange liquid.

(1E) -methyl {[2- (trifluoromethyl) -1,3-thiazol-5-yl] methyl}-from sulfide (B) using the same procedure described in Example III (C) above λ ⁴ -Sulfanilidenecyanamide was obtained as a pale yellow syrup.

Example VI. Preparation of 3- [6- (trifluoromethyl) pyridin-3-yl] tetrahydro-1H-1λ ⁴ -thien-1-ylidenecyanamide (6)

Tetrahydrothien-3-one (9.947 g, 97.37 mmol) was added to 250 mL Parm bomb. Triphenylphosphine (28.09 g, 108.0 mmol) was added followed by CH ₃ I (0.30 mL, 4.8 mmol) and dimethyl carbonate (10.0 mL, 119 mmol). The reactor was purged with nitrogen and then heated at 175 ° C. for 3 hours. The reaction mixture was cooled to room temperature and purified by Kugelrohr distillation to give 3-methylene-tetrahydrothiophene (7.65 g) as a colorless liquid containing the desired olefins with methanol and benzene. The desired olefin was used without further purification.

3-methylene-tetrahydrothiophene (5.88 g, as a mixture with benzene and methanol) was placed in 25 mL parvam with a magnetic stir bar introduced. Rh (CO) ₂ (acac) (149 mg, 0.58 mmol) and 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (xanthose) (355 mg, 0.61 mmol) as a solid Added. The reactor was sealed, purged with CO and pressurized to 350 psi. Hydrogen was then added to bring the total pressure to 700 psi. The reactor was heated to 80 ° C. with magnetic stirring for 14 hours. The reaction mixture was cooled to room temperature. GC-MS showed the presence of a single aldehyde regioisomer with benzene and methanol. There was no starting olefin. The solvent was removed in vacuo and the product (tetrahydrothien-3-yl acetaldehyde) was isolated as colorless liquid by distillation with cogel (50 ° C./0.01 mm) (1.1 g).

Pure tetrahydrothien-3-yl acetaldehyde (1.10 g, 8.45 mmol) was placed in a nitrogen purged vial. The vial was cooled in an ice bath and solid K ₂ CO ₃ (0.584 g, 4.23 mmol) was added. Pure pyrrolidone (1.70 mL) was added dropwise over 5 minutes. The ice bath was removed and the reaction mixture was stirred for 20 h under N ₂ . GC-MS showed clear formation of the desired enamine. The solid was washed four times with 10 ml ether. The combined ether extracts were evaporated in vacuo to yield intermediate enamine (1.617 g) as a pale yellow oil. 3-ethoxy-2-trifluoromethylpropenal (1.634 g, 9.72 mmol) was dissolved in anhydrous CH ₃ CN (5 mL) under nitrogen.

The solution was cooled in an ice bath. A solution of enamine (1.617 g) in 2 mL CH ₃ CN was added dropwise over 10 minutes. The ice bath was removed and the solution was allowed to come to room temperature and stirring continued for 2 hours. Ammonium acetate (1.407 g, 18.25 mmol) was added and the reaction mixture was refluxed under nitrogen for 1 hour. The solution was cooled to room temperature and CH ₃ CN was evaporated in vacuo. The resulting red oil was purified by column chromatography on silica using hexanes-ethyl acetate to give 5-tetrahydrothien-3-yl-2- (trifluoromethyl) pyridine (1.08 g; 52.3% as an orange crystalline solid. Yield).

(1E) -3- [6- (trifluoromethyl) pyridine from 5- (tetrahydrothien-3-yl) -2-trifluoromethylpyridine using the same procedure described in Example III (C) above. -3-yl] tetrahydro-1H-1λ ⁴ -thien-1-ylidenecyanamide (6) was obtained as off-white powder. The ¹ H NMR spectrum of the solid showed resonance for a 1: 1 mixture of diastereomers.

Example VII. Preparation of [(5-fluoro-6-chloropyridin-3-yl) methyl] (methyl) -λ ⁴ -sulfanylidenecyamide (7)

2-chloro-3-fluoro-5-methylpyridine (5.1 g, 35 mmol), N-bromosuccinimide (6.1 g, 35 mmol) and benzoylperoxide (0.16 g, 0.66) in carbon tetrachloride (100 mL) mmol) was refluxed overnight. Upon cooling, the solid was filtered off, the filtrate was concentrated and loaded onto a silica gel column eluting with 5% EtOAc in hexanes to afford 3.77 g of the desired 2-chloro-3-fluoro-5-bromomethylpyridine as a colorless oil. Obtained at 48%. GC-MS: calcd for C ₆ H ₄ BrClFN: 224.46. Found: 224.

2-Chloro-3-fluoro-5-methylthiomethylpyridine was obtained from 2-chloro-3-fluoro-5-bromomethylpyridine using the same procedure described in Example III (B) above. GC-MS: calcd for C ₇ H ₇ ClFNS: 191.66. Found: 191.

[(5-fluoro-6-chloropyridin-3-yl) methyl] methyl- from 2-chloro-3-fluoro-5-methylthiomethylpyridine using the same procedure described in Example III (C) above. λ ⁴ -sulfanylidenecyamide (7) was obtained as off-white solid. LC-MS: calcd for C ₈ H ₇ ClFN ₃ S [M + 1] ⁺ : 232.69. Found: 232.04.

Example VIII. Preparation of [(6- (1,1-difluoroethylpyridin-3-yl) methyl] (methyl) -λ ⁴ -sulfanylidenecyamide (8)

Diethylamino sulfonyltrifluoride (DAST) (25.8 g, 260 mmol) in a solution of 5-methyl-2-acetylpyridine (9.9 g, 73.3 mmol) in molecular sieve-dried CH ₂ Cl ₂ (150 mL). Was added at room temperature and the mixture was stirred at room temperature overnight. Additional DAST (12 g, 74 mmol) was added and reaction continued for at least 2 days, then additional DAST (3.8 g, 23 mmol) was added and reaction continued for another 3 days. After the reaction was slowly quenched with saturated NaHCO ₃ at 0 ° C., the organic phase was separated, dried over Na ₂ SO ₄ , filtered and concentrated. The residue was purified on silica gel eluting with 8% EtOAc (v / v) in hexanes to give 3.91 g of 2- (1,1-difluoroethyl) -5-methylpyridine (A) as a pale brown oil. Obtained in% yield. GC-MS: mass calcd. For C ₈ H ₉ F ₂ N [M] ⁺ 157. found 157.

2- (1,1-difluoroethyl) -5-methylpyridine (A) (2.0 g, 12.7 mmol), N-bromosuccinimide (2.2 g, 12.7 mmol) and benzoyl in carbon tetrachloride (100 mL) A mixture of peroxide (0.15 g, 0.63 mmol) was refluxed overnight. After the solid was removed by filtration, the filtrate was concentrated. The residue was redissolved in ethanol (40 mL) and sodium thiomethoxide (1.33 g, 19 mmol) was added at room temperature and stirred for 3 hours. The solvent was removed under reduced pressure and the remaining mixture was dissolved in CH ₂ Cl ₂ and water. After separation, the organic layer was dried over Na ₂ SO ₄ , filtered and concentrated. The crude product 2- (1,1-difluoroethyl) -5-methylthiomethylpyridine (B) was 94% pure on GC / MS and used directly in the next reaction without further purification. GC-MS: mass calcd. For C ₉ H ₁₁ F ₂ NS [M] ⁺ 203. found 203.

[(6- (1,1-difluoroethyl) from 2- (1,1-difluoroethyl) -5-methylthiolmethylpyridine (B) using the same procedure described in Example III (C) above. Pyridin-3-yl) methyl] (methyl) -λ ⁴ -sulfanylidenecyanamide (8) was obtained as a brownish solid LC-MS: mass calcd. For C ₁₀ H ₁₁ F ₂ N ₃ S [ M] ⁺ 243.28. Found [M + 1] ⁺ 244.11.

Example IX. Preparation of cis- [2- (6-chloropyridin-3-yl) cyclopentyl] (methyl) -λ ⁴ -sulfanylidenecyamide (9)

5-Bromo-2-chloropyridine (3.0 g, 15.6 mmol) was dissolved in diethyl ether (100 mL) in an oven-dried, nitrogen-flushed 250 mL round bottom flask and dried with a dry ice / acetone bath under nitrogen. Cooled in. n-BuLi (1.05 g, 16.4 mmol, 6.6 mL of a 2.5 M solution in hexane) was added via syringe and the orange heterogeneous mixture was stirred for 1 h. Cyclopentanone (1.3 g, 15.6 mmol) was added via syringe and the mixture was warmed to −20 ° C. and then quenched with 1 N HCl. The mixture was extracted with EtOAc and the organic extracts were washed with saturated NaHCO ₃ . The NaHCO ₃ wash is used to neutralize the first aqueous layer, the combined aqueous layers are extracted with additional EtOAc, the combined organic layers are dried (Na ₂ SO ₄ ), filtered, concentrated and flash silica gel chromatography (hexanes: EtOAc; 2 Purification by 1) gave 1- (6-chloropyridin-3-yl) cyclopentanol (2.33 g, 76%) as off-white solid: mp 92-93 ° C., LC / MS (ESI) m / z 197,

1- (6-chloropyridin-3-yl) cyclopentanol (2.1 g, 10.5 mmol) was treated with acetic acid (12 mL) and sulfuric acid (4 mL) and the mixture was heated to reflux for 30 minutes. After cooling to room temperature, ice and 2 N NaOH (180 mL) are added and the resulting tan precipitate is collected by filtration, washed with H ₂ O and dried to give 2-chloro-5- (cyclo) as a tan solid. Pent-1-enyl) pyridine (1.66 g, 88%) was obtained: mp 59-60 ° C., LC / MS (ESI) m / z 179,

2-chloro-5- (cyclopent-1-enyl) pyridine (1.5 g, 8.5 mmol) was dissolved in THF (30 mL) in an oven-dried, nitrogen-fluxed 250 mL round bottom flask and the resulting solution Was cooled in a dry ice / acetone bath under nitrogen. BH ₃ · THF complex (2.4 g, 28.0 mmol, 28 mL of a 1 M solution in THF) was added dropwise via syringe with stirring, and the mixture was slowly allowed to come to room temperature and stirred overnight. 2 N NaOH (15 mL), ethanol (15 mL) and 35% H ₂ O ₂ (10 mL) were added and the mixture was stirred for 0.5 h and then diluted with EtOAc and 1 N HCl. The layers were separated and the organic layer was washed with brine and aqueous NaHSO ₃ , dried over Na ₂ SO ₄ , filtered through celite and concentrated. Purification by flash chromatography (hexane: EtOAc / 10: 1 → 2: 1) by-product 2-chloro-5-cyclopentylpyridine (0.45 g, 29%) and 1- (6-chloropyridine-3- in elution order 1) cyclopentanol (0.44 g, 26%), then the desired product trans-2- (6-chloropyridin-3-yl) cyclopentanol (0.25 g, 15%) was obtained as a clear oil: LC / MS (ESI) m / z 197,

Trans-2- (6-chloropyridin-3-yl) cyclopentanol (0.225 g, 1.14 mmol) was dissolved in CH ₂ Cl ₂ (10 mL) in a 50 mL round bottom flask and the solution cooled in an ice bath under nitrogen. And treated with syringe with Et ₃ N (0.172 g, 1.71 mmol, 0.24 mL) and methanesulfonyl chloride (0.163 g, 1.42 mmol, 0.11 ml) with stirring. After 1 hour, TLC (hexane: EtOAc / 2: 1) showed complete conversion. The reaction mixture was concentrated in vacuo and then partitioned between EtOAc and 1N HCl. The layers were separated, the organics dried (Na ₂ SO ₄ ), filtered and concentrated to trans-methanesulfonic acid 2- (6-chloropyridin-3-yl) cyclopentyl ester (0.303 g, 97%) as an oil. Obtained: LC / MS (ESI) m / z 275,

Trans-methanesulfonic acid 2- (6-chloropyridin-3-yl) cyclopentyl ester (0.295 g, 1.07 mmol) was dissolved in EtOH (5 mL) in a 25 mL round bottom flask and cooled in an ice bath under nitrogen. Sodium methane thioleate (0.224 g, 3.20 mmol) was added all at once and the cloudy white mixture was brought to room temperature and stirred overnight. The mixture was diluted with EtOAc and brine and the layers separated. The organic layer was washed with brine, dried (Na ₂ SO ₄ ), filtered and concentrated. Purification by flash silica gel chromatography (hexane: EtOAc / 10: 1) gave cis-2-chloro-5- (2-methylthiocyclopentyl) pyridine (0.148 g, 61%) as an oil;

Cis- [2- (6-chloropyridin-3-yl) cyclopentyl] from cis-2-chloro-5- (2-methylthiocyclopentyl) pyridine using the same procedure described in Example III (C) above (Methyl) -λ ⁴ -sulfanylidenecyamide (9) was obtained as an oily 1: 1 mixture of diastereomers.

Example X. Preparation of [(4,6-dichloropyridin-3-yl) methyl] (methyl) -λ ⁴ -sulfanylidenecyamide (10)

To a stirred solution of ethyl 4,6-dichloronicotinate (8.8 g, 40 mmol) in anhydrous THF (75 mL) cooled in an ice bath was added dropwise a 1 M LiAlH ₄ solution (25 mL, 25 mmol) in THF. During the dropping, the temperature was not allowed to rise above 25 ° C. After the addition, the reaction was warmed to 40 ° C. for 15 minutes, cooled and quenched by successively dropwise addition of water (0.95 mL), 15% aqueous NaOH (0.95 mL) and water (1.85 mL). The mixture was filtered through celite, the filtrate was dried (MgSO ₄ ), passed through a short pad of silica gel and concentrated to give a red oil. The addition of ether (100 mL) gave a gummy precipitate immediately which was removed by filtration. The ether solution was left overnight at room temperature during which more precipitate formed and was removed again by filtration. The ether solution was concentrated and dried to give 3.25 g of the product 2,4-dichloro-5-hydroxy-methylpyridine in 46% yield as an almost colorless oily solid.

Starting material 2,4-dichloro-5-hydroxymethylpyridine (3.2 g, 18 mmol) was obtained as 2,4-dichloro-5-chloromethyl as a yellow oil using the same procedure as described in Example II (D) above. Converted to pyridine 2.O g (57% yield).

2,4-dichloro-5-methylthiomethylpyridine (2.0 g, 94% yield) was prepared in the same manner as described in Example I, Procedure A using 2,4-dichloro-5-chloromethylpyridine (2.0 g, 1.0 mmol) as a yellow oil.

[(4,6-Dichloropyridin-3-yl) methyl] (methyl) -λ ⁴ -sulfanylidene-cyanamide (10) was prepared using the same method as described in Example I (B). Prepared as a pale yellow gum from dichloro-5-methylthiomethylpyridine.

Example XI. Insecticide test

The compounds identified in the above examples were tested for cotton aphid and green peach aphid using the procedure described below.

Cotton aphid (Apis gopi) in leaf spray analysis Aphis gossypii Insecticide test for))

A squash with fully expanded cotyledon was trimmed to leave 1 cotyledon per plant and infested with cotton aphids (wingless adults and larvae) one day prior to chemical application. Each plant was examined prior to chemical application to ensure proper spread (30-70 aphids per plant). Compound (2 mg) was dissolved in 2 ml of acetone: methanol (1: 1) solvent to form 1000 ppm stock solution. The stock solution was diluted 5-fold with 0.025% Tween 20 in H ₂ O to give a 200 ppm solution. A serial 4-fold dilution was made from a 200 ppm solution using a dilution consisting of 80 parts of 0.025% Tween 20 in H ₂ O and 20 parts of acetone: methanol (1: 1) to produce lower concentrations (50, 12.5 and 3.13 ppm). The solution was prepared. A spray solution was applied using a hand held Devilbiss sprayer until it spilled on both sides of the pumpkin cotyledon. Four plants (4 repetitions) were used for each concentration of each compound. Reference plants (solvent test) were sprayed only with diluent. The treated plants were kept in a holding room at approximately 23 ° C. and 40% RH for 3 days and then the number of live aphids on each plant was recorded. Insecticidal activity was measured by percent control rate corrected using the Abbott correction equation and provided in Table 1 below:

Corrected% Control Rate = 100 * (X-Y) / X

(Where X = number of aphids alive on the solvent test plant,

        Y = number of live aphids on treated plants)

Peach hump aphid (Miss Persicae) in leaf spray analysis Myzus persicae Insecticide test for))

Cabbage seedlings grown in 3-inch pots with 2 to 3 small (3 to 5 cm) main leaves were used as test substrates. Seedlings were infested with 20 to 50 peach hump aphids (wingless larvae and larvae) 2-3 days before chemical application. Four seedlings were used for each treatment. Compound (2 mg) was dissolved in 2 ml of acetone: methanol (1: 1) solvent to form 1000 ppm stock solution. The stock solution was diluted 5-fold with 0.025% Tween 20 in H ₂ O to give 200 ppm of solution. A serial 4-fold dilution was made from a 200 ppm solution using a dilution consisting of 80 parts of 0.025% Tween 20 in H ₂ O and 20 parts of acetone: methanol (1: 1) to produce lower concentrations (50, 12.5 and 3.13 ppm). The solution was prepared. The solution was sprayed using a hand held Devilvis sprayer until it spilled on both sides of the cabbage leaf. Reference plants (solvent test) were sprayed only with diluent. Treated plants were graded after holding in a holding room at approximately 23 ° C. and 40% RH for 3 days. Evaluation was performed by counting the number of live aphids per plant under the microscope. Insecticidal activity was determined using the Abbott calibration:

Corrected% Control Rate = 100 * (X-Y) / X

(Where X = number of aphids alive on the solvent test plant,

        Y = number of live aphids on treated plants)

The percent control values corrected from the analysis are provided in Table 1 below.

CA 200 shows percent control at 200 ppm against cotton aphid in leaf spray test,

CA 50 shows percent control at 50 ppm against cotton aphid in leaf spray test,

GPA 200 shows percent control at 200 ppm against peach or aphid in leaf spray test,

GPA 50 shows percent control at 50 ppm against peach or aphids in the leaf spray test.

In each case of Table 1 above, the rating scale is as follows:

Insecticide Uses

The compounds of the present invention are useful for controlling invertebrates, including insects. Accordingly, the present invention also relates to a method for inhibiting an insect comprising applying an insect-suppressing amount of a compound of formula I directly to the place of the insect, the area to be protected or the insect to be controlled. The compounds of the present invention can also be used to control other invertebrate pests such as mites and nematodes.

"Place" of an insect or other pest is used herein to mean the environment in which they live or where their eggs exist, including the air surrounding the insect or other pest, the food they eat or the objects they contact. For example, an insect that eats, damages, or contacts edible, commodity, ornamental, grass, or ranch plants may be a seed, seedling or planted pruning, leaf, stem, fruit, grain and / or root of the plant before planting, or It can be controlled by applying the active compound to soil or other growth medium before or after planting the crop. In addition, protection of these plants against viral, fungal or bacterial diseases can be achieved indirectly through the control of juice-ingesting pests such as dusty, extinct, aphid and spider mites. Such plants include those that have been improved through conventional methods and genetically modified using modern biotechnology to obtain insect-tolerant, herbicide-tolerant, nutrition-enhancing and / or any other beneficial features.

The compound may also contain the active compound in or near textiles, paper, stored grains, seeds and other food, homes and other buildings, farms, ranches, zoos or other animals where humans and / or companions may reside. It is contemplated that the application may be useful for protecting the subject. Livestock, buildings or humans will be protected by using these compounds to control invertebrate and / or nematode pests that can carry parasitic or infectious diseases. Such pests include, for example, chiggers, mites, teeth, mosquitoes, flies, fleas and filaments. Non-agricultural applications also include invertebrate pest control in forests, fields, roadsides and railroad tracks.

The term "insect suppression" means reducing the number of live insects or reducing the number of viable insect eggs. The degree of reduction achieved by the compound depends, of course, on the rate of application of the compound, the particular compound employed and the target insect species used. At least the amount of inactivation should be used. The term “insect-inactivated amount” is used to describe an amount sufficient to cause a measurable decrease in the treated insect population. Generally, active compounds in amounts ranging from 1 to 1000 ppm by weight are used. For example, insects or other pests that can be inhibited include, but are not limited to:

Lepidoptera- Heliothis species, Helicoverpa species, Spodoptera species, Mythimna unipuncta , Agrotis ipsilon , Earias ) Species, Euxoa auxiliaris , Trichoplusia ni , Anticarsia gemmatalis , Rachiplusia nu , Plutella xylostella , Chilo species, Scirpophaga incertulas , Sesamia inferens , Cnaphalocrocis medinalis , Ostrinia nubilalis , Sidi Ah Po Monella.All (Cydia pomonella), carboxylic Posey or you ponen system (Carposina niponensis), O Come, toxins or PS (Adoxophyes orana), are are decided spill Ruth (Archips argyrospilus) kipseu the plate Miss heparanase (Pandemis heparana), Epi No thiazol Apo Sliema (Epinotia aporema), circulated Celia cancer acetabular Ella (Eupoecilia ambiguella), Kurobe cyano boat Lana (Lobesia botrana), poly chroman system Beate Ana (Polychrosis viteana), Peg Martino Pectinophora gossypiella , Pieris rapae , Phyllonorycter species, Leucoptera malifoliella , Phyllocnisitis citrella

Coleoptera- Diabrotica species, Leptinotarsa decemlineata , Oulema oryzae , Anthonomus grandis , Resor Hoptruss Lissorhoptrus oryzophilus , Agriotes spp., Melanotus communis , Popillia japonica , Cyclocephala spp., Tribolium spp.

Simultaneous Amok (Homoptera) - Apis (Aphis) species, American's Pere Chicago to (Myzus persicae), a Palo sipum (Rhopalosiphum) Ah species, disa piece Planta Guinea (Dysaphis plantaginea), Tok Thorpe Terra (Toxoptera) species, Macro Prizes Macrosiphum euphorbiae , Aulacorthum solani , Sitobion avenae , Metopolophium dirhodum , Schizaphis graminum , Brachycolus noxius , Nephotettix species, Nilaparvata lugens , Sogatella furcifera , Laodelfax striatellus ) bemi other Asian Bridge (Bemisia tabaci), the tree right Alessio des bar Fora Rio Room (Trialeurodes vaporariorum), Alessio right Deaths program rolre telra (Aleurodes proletella), Alessio right tree Seuss Seuss nose flow (Aleurothrixus floccosus), Speedy driver ohtuseu Pere Nishio Seuss (Quadraspidiotus perniciosus), Unas piece Yano linen sheath (Unaspis yanonensis), vertical plastic test Rubens (Ceroplastes rubens), sludge de-ah brother is Ella Tee (Aonidiella aurantii)

Hemiptera (Hemiptera) - Lee Goose (Lygus) species, Glass Gas Thermal Maura (Eurygaster maura), four growing corruption dulra (Nezara viridula), the piezo doruseu way dinghy (Piezodorus guildingi), Lev Toko Lisa Bari Accor Nice (Leptocorisa varicornis), Cimex lectularius , Cimex hemipterus

Thysanoptera- Frankliniella species, Thrips species, Scirtothrips dorsalis

Termites neck (Isoptera) - Retina Cooley Termez flaviviruses Fez (Reticulitermes flavipes), kopto Termez Formosa Augustine (Coptotermes formosanus), Retina Cooley Termez Vir Guinea Syracuse (Reticulitermes virginicus), hetero-Thermes aureus (Heterotermes aureus ), Reticulitermes hesperus , Coptotermes frenchii , Shedorhinotermes species, Reticulitermes santonensis , Reticulitermes sansperensis ( Reticulitermes grassei ), Reticulitermes banyulensis , Reticulitermes speratus , Reticulitermes hageni , Reticulitermes tibialis tibialis , Zootermopsis species, Incisitermes species, Marginite rmes) species, mark Termez (Macrotermes) species, micro-vertical Termez (Microcerotermes) species, micro-Thermes (Microtermes) species

Diptera- Liriomyza species, Musca domestica , Aedes species, Culex species, Anopheles species, Fannia species, Stomoxys Species

Logging (Hymenoptera) - yirido MIR Mex After mm's (Iridomyrmex humilis), Soleil Smirnoff sheath (Solenopsis) species, mono mode Solarium Pharaoh varnish (Monomorium pharaonis), Atta (Atta) species, pogo furnace Mir Mex (Pogonomyrmex) species, camphor Camponotus species, Monomorium species, Tapinoma sessile , Tetramorium species, Xylocapa species, Vespula species, Polystes ( Polistes ) Species

Mallorphaga (chewing lice)

Anoplura (sucking lice) -Pthirus pubis , Pediculus species

Orthoptera (locust, cricket) -Melanoplus species, Locusta migratoria , Schistocerca gregaria , Gryllotalpidae ( Ground dog).

Wheeltodea (wheels)-Blatta orientalis , Blattella germanica , Periplaneta americana , Supella longipalpa , Periplaneta Periplaneta australasiae , Periplaneta brunnea , Parcoblatta pennsylvanica , Periplaneta fuliginosa , Pycnoscelus surinamen

Siphonaptera- Ctenophalides species, Pulex irritans

Acarina- Tetranychus species, Panonychus species, Eotetranychus carpini , Phyllocoptruta oleivora , Aculus apeus pelekassi , Brevipalpus phoenicis , Boophilus species, Dermacentor variabilis , Rhipicephalus sanguineus , Amblyomma americanum americanum ), Ixodes species, Notoedres cati , Sarcoptes scabiei , Dermatophagoides species

Nematoda- Dirofilaria immitis , Meloidogyne species, Heterodera species, Hoplolaimus columbus , Belonolaimus species, Pratylenkus ( Pratylenchus ) species, Rotylenchus reniformis , Criconemella ornata , Ditylenchus species, Apelenchoides besseyi , Hirshmanniela ( Hirschmanniella ) species

Composition

Compounds of the present invention are important embodiments of the present invention and are applied in the form of compositions comprising a compound of the present invention and a botanically acceptable inert carrier. Pest control is sprayed, topically treated, gels, seed coated, microencapsulated, penetrated, absorbed, bait, ear tags, bolus, fogger, fumigant aerosols, powders and many other forms of the present invention. Is achieved by application. The composition is a concentrated solid or liquid formulation dispersed in water for application, or a powder or granules which are applied without further treatment. The compositions are prepared according to procedures and prescriptions common in the field of agricultural chemistry, but are new and important because the compounds of the present invention are present in the compositions. However, some explanations will be provided regarding the formulation of the composition to ensure that agrochemists can easily produce any desired composition.

The dispersion in which the compound is applied is most often an aqueous suspension or emulsion prepared from concentrated formulations of the compound. Such water-soluble, water-suspendable or emulsifiable preparations are solids, commonly known as wettable powders or liquids, commonly known as emulsifiable concentrates or aqueous suspensions. Wettable powders that can be compressed to form water dispersible granules include a homogeneous mixture of active compound, inert carrier, and surfactant. The concentration of the active compound is usually 10 to 90% by weight. Inert carriers are typically selected from attapulgite clay, montmorillonite clay, diatomaceous earth or purified silicate. Effective surfactants that comprise 0.5% to 10% of the wettable powders are nonionic surfactants such as sulfonated lignin, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and ethylene oxide adducts of alkyl phenols. It is found in the middle.

The emulsifiable concentrate of the compound is dissolved in an inert carrier which is a water miscible solvent or a mixture of water-immiscible organic solvents and an emulsifier, such as at a convenient concentration of 50 to 500 g per liter of liquid corresponding to 10% to 50%, for example. Compound. Useful organic solvents include aromatic solvents, in particular xylene, and petroleum fractions, especially high-boiling naphthalene and olefinic fractions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as terpene-based solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are selected from conventional anionic and / or nonionic surfactants such as those described above.

Aqueous suspensions include suspensions of the water-insoluble compounds of the invention dispersed in an aqueous vehicle at concentrations ranging from 5 to 50% by weight. Suspensions are prepared by finely grinding a compound and mixing it vigorously in a vehicle consisting of water and a surfactant selected from the same kind as described above. Inorganic salts and inert ingredients such as synthetic or natural gums may also be added to increase the density and viscosity of the aqueous vehicle. It is often most effective to prepare an aqueous mixture and homogenize it in a device such as a sand mill, ball mill or piston type homogenizer to simultaneously grind and mix the compounds.

The compounds can also be applied as granular compositions, which are particularly useful for application to soil. Granular compositions typically contain from 0.5 to 10% by weight of the compound, wholly or mostly dispersed in an inert carrier consisting of clay or similar inexpensive materials. Such compositions are conventionally prepared by dissolving the compound in a suitable solvent and applying it to a preformed granular carrier with a suitable particle size in the range of 0.5 to 3 mm. Such compositions can also be formulated by preparing a dough or paste of a carrier and a compound and grinding and drying it to obtain the desired granular particle size.

Powders containing the compounds are prepared simply by homogeneous mixing of the compounds in powdered form with suitable powdery agricultural carriers such as kaolin clay and powdered ash. The powder may suitably contain 1% to 10% of the compound.

If desired for any reason, it is likewise practical to apply the compound in the form of a solution in a suitable organic solvent which is typically a mild petroleum oil, such as spray oil, which is widely used in agricultural chemistry.

Pesticides and acaricides are generally applied in the form of a dispersion of the active ingredient in a liquid carrier. It is common to refer to the application rate in terms of the concentration of the active ingredient in the carrier. The most widely used carrier is water.

The compounds of the present invention may also be applied in the form of aerosol compositions. In such compositions the active compound is dissolved or dispersed in an inert carrier which is a pressure-producing propellant mixture. The aerosol composition is packaged in a container in which the mixture is dispensed through an atomization valve. The propellant mixture comprises a low boiling halocarbon that can be mixed with an organic solvent, or an aqueous suspension pressurized with an inert gas or gaseous hydrocarbon.

The actual amount of compound to be applied in place of insects and ticks is not critical and can be readily determined by one skilled in the art in view of the above examples. In general, it is expected that compound concentrations of 10 to 5000 ppm by weight will provide good control. For many compounds, a concentration of 100 to 1500 ppm will be sufficient.

The place where the compound is to be applied may be any place where insects or mites live, such as vegetable crops, fruit and nut trees, grapevines, ornamental plants, livestock, the interior or exterior surfaces of buildings, and the soil around buildings. .

Because of the inherent poisoning resistance of insect eggs, repeated application may be desirable to control newly generated larvae as in the case of other known insecticides and acaricides.

Penetration shifts of the compounds of the present invention in plants can be used to control pests in one part of the plant by applying the compound to other parts of the plant. For example, the control of leaf-eating insects can be controlled by rip irrigation or furrow application, or by seed treatment before planting. Seed treatment can be applied to all types of seeds, including those that germinate genetically modified plants to express particular characteristics. Representative examples include seeds expressing proteins or other pesticidal proteins toxic to invertebrate pests such as Bacillus thuringiensis , seeds expressing herbicide tolerance, such as "Roundup Ready". Seeds, or seeds with "stacked" external genes that express pesticidal proteins, producer resistance, nutrition-enhancing and / or any other beneficial features are included.

Insecticidal bait compositions consisting of the compounds of the present invention and handouts and / or ingestion promoters can be used to increase the efficacy of insecticides against insect pests in devices such as traps and baits. Bait compositions are solid, semi-solid (including gel) or liquid bait matrices comprising an accelerator and at least one non-microencapsulated or microencapsulated pesticide in an amount effective to act as a biocide.

The compounds of the present invention (Formula I) are often applied in combination with one or more other pesticides or fungicides or herbicides to achieve control of a wide range of pest diseases and weeds. When used in combination with other insecticides or fungicides or herbicides, the presently claimed compounds are formulated with other insecticides or fungicides or herbicides, tank mixed with other insecticides or fungicides or herbicides, or with other pesticides or fungicides or herbicides It can be applied sequentially.

Some pesticides that may advantageously be used in combination with the compounds of the present invention include antibiotic insecticides such as allosamidine and turingienens; Macrocyclic lactone insecticides such as spinosad, spinetoram and other spinosins, including 21-butenyl spinosine and derivatives thereof; Avermectin insecticides such as abamectin, doramectin, emamectin, eprinomectin, ivermectin and celamectin; Milbemicin insecticides such as lepimethin, milbemectin, milbamycin oxime and moxidecin; Arsenic insecticides such as calcium arsenate, copper acetoarsenite, copper arsenate, lead arsenate, potassium arsenite and sodium arsenite; Biological insecticides such as Bacillus popilliae , b. B. sphaericus , b. B. thuringiensis subsp. Aizawai , b. B. thuringiensis subsp. Kurstakiy , b. Turin-based N-Sys sub-species tene brioche Nice (B. thuringiensis subsp. Tenebrionis), non Augustus Bridge Beria Ana (Beauveria bassiana), Cydia Four Monella.All (Cydia pomonella) granules disease virus, Douglas fir tusok moth (Douglas fir tussock moth) NPV , Gypsy moth NPV, Helicoverpa zea NPV, Indian meal moth granulopathy virus, Metarhizium anisopliae , Nosema locustae ), Paecilomyces fumosoroseus , blood. P. lilacinus , Photorhabdus luminescens , Spodoptera exigua NPV, trypsin-regulated austik factor, Xenorhabdus nematophilus and X. Bobieni (X. bovienii), plant incorporated protective insecticides such as Cry1Ab, Cry1Ac, Cry1F, Cry1A.105, Cry2Ab2, Cry3A, mir Cry3A, Cry3Bb1, Cry34, Cry35 and VIP3A; Vegetable insecticides such as anabacin, azadirachtin, d-limonene, nicotine, pyrethrin, cinerine, cinerine I, cinerine II, jasminolin 1, jasmoline II, pyrethrin I, pyrethrin II, quacia , Rotenone, liana, and sabadilla; Carbamate insecticides such as bendiocarb and carbaryl; Benzofuranyl methylcarbamate insecticides such as benfuracarb, carbofuran, carbosulfan, decarbofuran and furaiocarb; Dimethylcarbamate insecticides such as dimitane, dimethylran, hiquincarb and pyrimicab; Oxime carbamate insecticides such as alaniccarb, aldicarb, aldoxicarb, butocarboxim, butoxycarbsim, metomil, nitrilecarb, oxamyl, tazimcarb, thiocarsim, thio Dicarb and thiophanox; Phenyl methylcarbamate insecticides such as alixiccarb, aminocarb, bufencarb, butacarb, carbanolate, clotocarb, dicresyl, dioxacarb, EMPC, thiophencarb, Penetacarb, phenobucarb, isoprocarb, methiocarb, metholcarb, mexacarbate, promasil, promecarb, propoxal, trimetacarb, XMC and xylylcarb; Dinitrophenol insecticides such as dinex, dinoprop, dinosam and DNOC; Fluorine insecticides such as barium hexafluoride, creolite, sodium fluoride, sodium hexafluoride and sulfluramide; Formamidine insecticides such as amitraz, chlordimethform, formmethate and formparanate; Fumigation insecticides such as acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform, chloropicrine, para-dichlorobenzene, 1,2-dichloropropane, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, hydrogen cyanide, iodomethane , Methyl bromide, methylchloroform, methylene chloride, naphthalene, phosphine, sulfuryl fluoride and tetrachloroethane; Inorganic insecticides such as borax, calcium polysulfide, copper oleate, mercury chloride, potassium thiocyanate and sodium thiocyanate; Chitin synthesis inhibitors such as bistrifluron, buprofezin, chlorfluazuron, cyromazine, diflubenzuron, fluxycloxone, flufenoxuron, hexaflumuron, lufenuron, novaluron, nobiflumuron, Fenfluron, teflubenzuron and triflumuron; Larvae hormone analogs such as epophenonane, phenoxycarb, hydroprene, quinoprene, metoprene, pyriproxyfen and triprene; Larvae hormones such as larvae hormones I, larvae hormones II and larvae hormones III; Metabolic hormone agonists such as chromafenozide, halofenozide, methoxyphenozide and tebufenozide; Metamorphic hormones such as α-ecdysone and ecdysterone; Metamorphic inhibitors such as diophenolrans; Precosenes such as precocene I, precocene II and precocene III; Unclassified insect growth regulators such as dicyclanil; Neracetoxin-like insecticides such as benzaltab, cartab, thiocyllam and thiosulfab; Nicotinoid insecticides such as flonicamid; Nitroguanidine insecticides such as clothianidine, dinotefuran, imidacloprid and thiamethoxam; Nitromethylene insecticides such as nitenpyram and nithiazine; Pyridylmethylamine insecticides such as acetamiprid, imidacloprid, nitenpyram and tiacloprid; Organochlorine insecticides such as bromo-DDT, campechlor, DDT, pp'-DDT, ethyl-DDD, HCH, gamma-HCH, lindane, methoxycyclo, pentachlorophenol and TDE; Cyclodiene insecticides such as aldrin, bromocycline, chlorbicylene, chlordan, chlordecone, dieldrin, dilor, endosulfan, endrin, HEOD, heptachlor, HHDN, isobenzane, isodrin, kelevane and Mirex; Organophosphate insecticides such as bromfenbinfos, chlorfenbinfos, crotoxyfoss, dichlorbose, dicrotophos, dimethylbinfos, phosphate, heptenofos, metocrotophos, mevinphos, monocrotophos, nal Red, naphthalophos, phosphamidone, propaphos, TEPP and tetrachlorbinfoss; Organothiophosphate insecticides such as dioxabenzophosphate, phosphmethylene and pentoate; Aliphatic organothiophosphate insecticides such as acethione, amitone, cardusafos, chlorethoxyforce, chlormephos, demepion, demepion-O, demepion-S, demetone, demetone-O, Demethone-S, Demethone-methyl, Demethone-O-methyl, Demethone-S-methyl, Demethone-S-methylsulfone, Disulfonone, Ethion, Etopropos, IPSP, Isothioate, Malathion , Methacryfoss, oxydemethone-methyl, oxydeprofos, oxydisulfotone, forate, sulfotep, terbufos and thiomethone; Aliphatic amide organothiophosphate insecticides such as amidithione, cyantoate, dimethate, etoate-methyl, formotene, mecarbam, ometoate, protoate, caffeamide and bamidothione; Oxime organothiophosphate insecticides such as chlorpoxime, bombard and bombard-methyl; Heterocyclic organothiophosphate insecticides such as azametiphos, coomaphos, cumitoate, dioxathione, endothion, menazone, morphothione, posalon, pyraclophos, pyridapention and quinothione; Benzothiopyrans organothiophosphate insecticides such as diticrophos and ticlophos; Benzotriazine organothiophosphate insecticides such as azineforce-ethyl and azineforce-methyl; Isoindole organothiophosphate insecticides such as dialilifos and phosmet; Isoxazole organothiophosphate insecticides such as isoxationone and zolapropos; Pyrazolopyrimidine organothiophosphate insecticides such as chlorprazofos and pyrazophos; Pyridine organothiophosphate insecticides such as chlorpyrifos and chlorpyrifos-methyl; Pyrimidine organothiophosphate insecticides such as butathioforce, diazinon, etrimforce, relimfoss, pyrimifos-ethyl, pyrimifos-methyl, primidose, pyrimitate and tebupyrimfoss; Quinoxaline organothiophosphate insecticides such as quinalforce and quinalfos-methyl; Thiadiazole organothiophosphate insecticides such as atidathione, ritidathione, metidathione and protidalthione; Triazole organothiophosphate insecticides such as isazofoss and triazofoss; Phenyl organothiophosphate insecticides such as azotoate, bromophos, bromophos-ethyl, carbophenothione, chlorthiophos, cyanophos, cioate, dicaptone, diclopentione, etaphos, palm Pour, Penchlorphos, Phenylthorion Pensulfothione, Pention, Pention-Ethyl, Heteroforce, Zodfenforce, Mesulfenforce, Parathion, Parathion-Methyl, Pencapton, Phosphochlor, Propenophosphate, Pro Thiophos, sulprofos, temefos, trichlormetafos-3, and trifenophos; Phosphonate insecticides such as butonate and trichlorphone; Phosphonothioate insecticides such as mecarphone; Phenyl ethylphosphonothioate insecticides such as phonophos and trichloronat; Phenyl phenylphosphonothioate insecticides such as cyanophenfos, EPN and leptophos; Phosphoramidate insecticides such as crufomate, phenamifos, postetitan, mephospolan, phospholane and pyrimetafoss; Phosphoramidothioate insecticides such as acetate, isocarbophos, isopenfos, metamidose, and propetafoam; Phosphorodiamide insecticides such as dimepox, marzipox, mifapox and shuradan; Oxadiazine insecticides such as indoxacarb; Phthalimide insecticides such as dialilifos, phosmet and tetramethrin; Pyrazole insecticides such as acetoprole, etiprolol, fipronil, pyraflulol, pyriprolol, tebufenpyrad, tolfenpyrad and vaniliprolol; Pyrethroid ester insecticides such as acrinatrin, alletrin, bioallytrin, barthrin, bifenthrin, bioethanomethrin, cicletrin, cycloprotrin, cyfluthrin, beta-cifluthrin, sihal Lotrin, gamma-cyhalothrin, lambda-cyhalothrin, cifermethrin, alpha-cifermethrin, beta-cifermethrin, theta-cifermethrin, zeta-cifermethrin, cifenotrine, deltamethrin, dimeflute Lean, dimethrin, empentrin, fenflutrin, phenpytrin, fenpropartin, fenvalrate, esfenvalrate, flucitrinate, fluvalinate, tau-fluvalinate, furtrerin, Imiprotrin, metofluthrin, permethrin, biopermethrin, trispermethrin, phenotrin, praletrin, profluthrin, pyresmethrin, resmethrin, bioresmethrin, cismethrin, tefluthrin, Teraletrin, Tetramethrin, Tralomethrin and Trat Lanceflutrin; Pyrethroid ether insecticides such as etofenprox, flufenprox, halfenprox, protrifenbut and silafluorene; Pyrimidinamine insecticides such as flufenerim and pyrimidipene; Pyrrole insecticides such as chlorfenapyr; Tetronic acid insecticides such as spirodiclofen, spiromesifen and spirotetramat; Thiourea insecticides such as diafenthiuron; Urea insecticides such as flucofuron and sulcofuron; And unclassified insecticides such as AKD-3088, Chloxanthel, Crotamiton, Cyflumetofen, E2Y45, EXD, Penazaflor, Penazaquin, Phenoxa Cream, Phenpyroximate, FKI-1033, Flubendiamide, HGW86, Hydramethylnon, IKI-2002, Isoprothiolane, Malonoben, Metaflumizone, Metoxadiazone, Niflulidide, NNI-9850, NNI-O1O1, Pimetrozine, Pyridaben, Pyridalyl, Cue Side, lapoxanide, linacyrpyre, SYJ-159, triarate and triamate, and any combination thereof.

Some fungicides that can be advantageously used in combination with the compounds of the invention include 2- (thiocyanatomethylthio) benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, Ampelomyces ), Quisqualis , azaconazole , azoxystrobin, Baccilus subtilis , benalacyl , benomil , benthiavalicarb -isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonate, Biphenyl, Bismerthiazole, Vitertanol, Blastisidin-S, Borax, Bordeaux mixture, Boscalid, Bromuconazole, Buptrimate, Calcium Polysulfide, Captapol, Captan, Cart Bendazim, carboxycin, capropamide, carbon, chloronep, chlorothalonil, clozolinate, coniothirium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (trivalent base), Cuprous oxide, cyazopamide, cyflufen Mead, cymoxanyl, ciproconazole, ciprodinyl, dazomet, devacarb, diammonium ethylenebis- (dithiocarbamate), diclofluanide, dichlorophene, diclocimet, diclomezin , Dichloran, dietofencarb, difenokazole, dipfenquat ion, diflumethorim, dimethomorph, dimoxistrobin, diconazole, dinconazole-M, dinobuton, dinocap, di Phenylamine, Dithianon, Dodemorph, Dodemorph Acetate, Dodine, Dodine Free Base, Ediffene Force, Epoxyconazole, Ethaboxam, Ethoxyquine, Etridazole, Pamoxadon, Phenamidone, Phenarimol , Fenbuconazole, fenfuram, phenhexamide, phenoxanyl, fenpiclonil, phenpropidine, fenpropimolp, fentin, fentin acetate, fentin hydroxide, perbam, perimzone, fluazinam, Fludioxonil, flumorph, fluoropicolide, fluoroimide, fluoxastrobin, flu Luquinconazole, flusilazole, flusulfamid, flutolanil, flutriafol, polpet, formaldehyde, pocetyl, pocetyl-aluminum, fuberidazole, furalacyl, furamepyr, guaztine, gu Azatin acetate, GY-81, hexachlorobenzene, hexaconazole, himexazole, imazaryl, imazalyl sulfate, imibenconazole, iminottadine, iminottadine triacetate, iminottadine tris (albesylate) , Ifconazole, Ifprobenfos, Iprodione, Iprovalicab, Isoprothiolane, Kasugamycin, Kasugamycin Hydrochloride Hydrate, Cresoxim-methyl, Mancoper, Mancozeb, Maneb, Mepanipyrim, Mepronyl, mercuric chloride, mercuric oxide, mercuric chloride, metallaxyl, mephenoxam, metallaxyl-M, metam, metham-ammonium, metam-potassium, metam-sodium, metconazole, metasulfocar Bromine, methyl iodide, methyl isothiocyanate, meth Tiram, metominostrobin, methrafenone, midiomycin, myclobutanyl, nabam, nitrotal-isopropyl, noarimol, octylinone, opurase, oleic acid (fatty acid), orissastrobin, oxa Dixyl, auxin-copper, oxpoconazole fumarate, oxycarboxycin, pefurazoate, fenconazole, pensicuron, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalate Reed, peacock cystrobin, polyoxine B, phospholioxine, polyoxolin, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procmidone, propamocarb, propamocarb hydrochloride , Propiconazole, propineb, proquinazide, prothioconazole, pyraclostrobin, pyrazophos, pyributycarb, pyrifenox, pyrimethanyl, pyroquilon, quinocamine, quinoxyphene, Quintozen, Reinutree Reynoutria sachalinensis extract, silthiofam, cimeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z071, tar oil, tebuconazole, Tecnazen, Tetraconazole, Tiabendazole, Tifluzamide, Thiophanate-Methyl, Thiram, Tiadinyl, Tollclofos-Methyl, Tolyluluanide, Triadimefon, Triadimenol, Triazoxide , Tricyclazole, tridemorph, tripleoxystrobin, tripleluminazole, tripolin, triticonazole, validamycin, vinclozoline, geneb, zeram, homamide, Candida oleophila, Fusarium oxysporum, Gliocladium species, Phlebiopsis gigantean, Streptomyces griseoviridis, Trichoderma species, ( RS) -N- (3,5-dichlorofe Nil) -2- (methoxymethyl) -succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4- Dinitronaphthalene, 1-chloro-2-nitropropane, 2- (2-heptadecyl-2-imidazolin-1-yl) ethanol, 2,3-dihydro-5-phenyl-1,4-diti- Phosphorus 1,1,4,4-tetraoxide, 2-methoxyethyl mercury acetate, 2-methoxyethyl mercury chloride, 2-methoxyethyl mercury silicate, 3- (4-chlorophenyl) -5-methylrodinine , 4- (2-nitroprop-1-enyl) phenyl thiocyanate me: ampropyl phos, anilazine, azitiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron , Benzamacryl; Benzamacryl-isobutyl, benzamorph, vinapacryl, bis (methylmercury) sulfate, bis (tributyltin) oxide, butiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, Clobenthiazone, chloraniformethane, chlorfenazole, chlorquinox, klimbazole, copper bis (3-phenylsalicylate), copper zinc chromate, cupraneb, cupric hydrazinium sulfate, cuprobam , Cyclafuramide, cypendazole, cipropuram, decapentin, diclones, diclozoline, diclobutrazole, dimethymolol, dinoctone, dinosulphone, dinoterborn, dipyrithione, ditalimfoss, dodi Sin, drazosolone, EBP, ESBP, etaconazole, etem, etirim, phenaminosulf, phenanil, phenythropan, fluorotrimazole, furcarbanyl, furconazole, furconazole-cis, purmethicol Rocks, furophanate, gliodine, griseofulvin, halakry Nate, Hercules 3944, Hexylthiophos, ICIA0858, Isofamphos, Isovaledion, Mebenyl, Mecarbinzide, Metazoxolone, Metfuroxam, Methylmercury dicyanamide, Metsulfobox, Milnep , Mucochloric anhydride, myclozoline, N-3,5-dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, N-ethyl mercurio-4-toluenesulfonanilide, nickel bis (Dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosphodifen, prothiocarb; Prothiocarb hydrochloride, pyracarbide, pyridinitrile, pyroxcyclo, pyroxifur, quinacetol; Quinacetol Sulfate, Quinazamide, Quinconazole, Rabenzazole, Salicylate, SSF-109, Sultropene, Tecoram, Thiadifluor, Tsiofene, Thiochlorfenpime, Thiophanate, Thioquinox, Thyoxymid, triamifos, triarimol, triazbutyl, trichlamide, urbaside, XRD-563 and zarylamide, and any combination thereof.

Some herbicides that may be used with the compounds of the present invention include amide herbicides such as alidochlor, beflubutamide, benzadox, benzipyram, bromobutide, carfenstrol, CDEA, chlortiamide, ciprazole, dimethe Namid, dimethenamid-P, diphenamide, epronaz, etnipromid, pentrazamide, flupoxam, pomessafen, halosafene, isocarbamide, isoxaben, napropamide, naph Talam, fetoxamide, propizamide, quinonamide and tebutam; Anilide herbicides such as chloranocryl, cisanilide, clomeprop, cipromid, diflufenican, etobenzanide, phenasulam, flufenacet, flufenican, mefenacet, mefluidide, metamime Popes, monalilides, naproanilides, pentanochlor, picolinafen and propanyl; Arylalanine herbicides such as benzoylprop, flamprop and flamprop-M; Chloroacetanilide herbicides such as acetochlor, alachlor, butachlor, butenachlor, delachlor, dietathyl, dimethachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor , Propisochlor, prinachlor, terbuchlor, tenylchlor and xylachlor; Sulfonanilide herbicides such as benzofluor, perfluidone, pyrimisulfan and profluazole; Sulfonamide herbicides such as asulam, carbasulam, penasulam and oryzaline; Antibiotic herbicides such as villanafoss; Benzoic acid herbicides such as chlorambene, dicamba, 2,3,6-TBA and tricamba; Pyrimidinyloxybenzoic acid herbicides such as bispyribac and pyriminobac; Pyrimidinylthiobenzoic acid herbicides such as pyrithiobac; Phthalic acid herbicides such as chlortal; Picolinic acid herbicides such as aminopyralide, clopyralide and picloram; Quinolinecarboxylic acid herbicides such as quinclolac and quinmerac; Arsenic herbicides such as cacodylic acid, CMA, DSMA, hexaflulate, MAA, MAMA, MSMA, potassium arsenite and sodium arsenite; Benzoylcyclohexanedione herbicides such as mesotrione, sulcotrione, tefuryltrione and tembotrione; Benzofuranyl alkylsulfonate herbicides such as benfuresate and etofumesate; Carbamate herbicides such as asulam, carboxazole chlorprocarb, dichlormate, phenasulam, carbutylate and terbucarb; Carvanylate herbicides such as barban, BCPC, carbasulam, carbetamid, CEPC, chlorbufam, chlorprofam, CPPC, desmedipham, phenisopam, phenmedipham, phenmedipham-ethyl, profam and Swept; Cyclohexene oxime herbicides such as alkoxydim, butoxydim, cletodim, cloprodimim, cycloxydim, propoxydim, cetoxydim, tetraproxydim and tralcoxysid; Cyclopropylisoxazole herbicides such as isoxachlortol and isoxaplitol; Dicarboximide herbicides such as benzfendizone, cinidon-ethyl, flumezin, flumichlorak, flumioxazine and flumipropine; Dinitroaniline herbicides such as benfluraline, butyralline, dinitramine, etaflularine, fluchlorine, isoprophalin, metalpropaloline, nitraline, oryzaline, pendimethalin, prodiamine, profluralin and Trituralin; Dinitrophenol herbicides such as dinophenate, dinoprop, dinosam, dinocept, dinoterb, DNOC, ethinophene and medinaterb; Diphenyl ether herbicides such as ethoxyphene; Nitrophenyl ether herbicides such as acifluorfen, acloniphene, biphenox, clomethoxyphene, clonitrofen, ethnipromid, fluorodiphene, fluoroglycopene, fluoronitrophene, pomesafen, furyloxy Pens, halosafen, lactofen, nitrofen, nitrofluorfen and oxyfluorfen; Dithiocarbamate preparations such as dazomet and metham; Halogenated aliphatic herbicides such as allolac, chlorophone, dalapon, flupropanoate, hexachloroacetone, iodomethane, methyl bromide, monochloroacetic acid, SMA and TCA; Imidazolinone herbicides such as imazamethabenz, imazamox, imazapic, imazapyr, imazaquin and imazetapyr; Inorganic herbicides such as ammonium sulfamate, borax, calcium chlorate, copper sulfate, ferrous sulfate, potassium azide, potassium cyanide, sodium azide, sodium chlorate and sulfuric acid; Nitrile herbicides such as bromobonyl, bromoxynil, chloroxynyl, dichlorobenyl, iodobonyl, ioxyyl and pyraclonyl; Organophosphorus preparations such as amiprophos-methyl, anilofos, bensulfide, villanafos, butamifos, 2,4-DEP, DMPA, EBEP, fosamine, glufosinate, glyphosate and pipero Force; Phenoxy herbicides such as bromophenoxime, clomeprop, 2,4-DEB, 2,4-DEP, difenofene, disul, erbon, etnipromid, penteracol and tripofsim; Phenoxyacetic herbicides such as 4-CPA, 2,4-D, 3,4-DA, MCPA, MCPA-thioethyl and 2,4,5-T; Phenoxybutyric acid herbicides such as 4-CPB, 2,4-DB, 3,4-DB, MCPB and 2,4,5-TB; Phenoxypropinic acid herbicides such as cloprof, 4-CPP, dicloprop, dicloprop-P, 3,4-DP, phenofprop, mecoprop and mecoprop-P; Aryloxyphenoxypropinic acid herbicides such as clorazifop, clodinapov, clopov, sihalofop, diclopov, phenoxaprop, phenoxaprop-P, pentiaprop, fluazifop, flu Azipop-P, haloxy-pop, haloxy-pop-P, isoxapyrifop, metamipop, propaquizapop, quizalopope, quizalopope-P and tripope; Phenylenediamine herbicides such as dinitramine and prodiamine; Pyrazolyl herbicides such as benzophenaf, pyrazolinate, pyrasulfol, pyrazoxifen, pyroxasulfone and toppramezone; Pyrazolylphenyl herbicides such as fluazolate and pyraflufen; Pyridazine herbicides such as cradazine, pyridafol and pyridate; Pyridazinone herbicides such as brompyrazone, chloridazone, dimidazone, flufenpyr, metflurazone, norflurazone, oxapirazone and pidanone; Pyridine herbicides such as aminopyralides, cliodinates, clopyralides, dithiopyr, fluoroxypyr, halidedines, picloram, picolinafen, pyrichlor, thiazopyr and triclopyr; Pyrimidinediamine herbicides such as ifrimidam and thiochlorim; Quaternary ammonium herbicides such as ciperquat, diethamquat, dipfenquat, diquat, morphamput and paraquat; Thiocarbamate herbicides such as butyrate, cycloate, di-acrylate, EPTC, esprocarb, ethiolate, isopolyate, methiobencarb, molinate, orbencarb, pebulate, Prosulfocarb, pyributycarb, sulfalate, thiobencarb, thiocarbazyl, tri-allate and benolate; Thiocarbonate herbicides such as dimexano, EXD and proxane; Thiourea herbicides such as methiuron; Triazine herbicides such as diproperine, triazulflam and trihydroxytriazine; Chlorotriazine herbicides such as atrazine, chlorazine, cyanazine, cipraazine, eglinazine, ipazine, mesoprazine, prosazine, proglyazine, propazine, cebutylazine, simazine, terbutylazine and Triethazine; Methoxytriazine herbicides such as atraton, metomethone, promethone, secbumethone, cimetone and terbumethone; Methylthiotriazine herbicides such as amethrin, aziprotrin, cyanathrin, desmethrin, dimethatrin, metoprotrin, promethrin, cymetrin and terbutryn; Triazinone herbicides such as amethidione, amibuzin, hexazinone, isomethiazine, metamitrone and methibuzin; Triazole herbicides such as amitrol, carfenstrol, epronaz and flupoxam; Triazolone herbicides such as amicarbazone, bencarbazone, carpentrazone, flucarbazone, propoxycarbazone, sulfentrazone and thiencarbazone-methyl; Triazolopyrimidine herbicides such as chloransulam, diclosulam, florasulam, flumetsulam, metosulam, phenoxsulam and pyroxsulam; Uracil herbicides such as butafenacyl, bromacil, flupropacyl, isosil, lenacil and terbasil; 3-phenyluracil; Urea herbicides such as benzthiazuron, cumyluron, cyclluron, dichloralurea, diflufenzopyr, isonoruron, isouron, metabenzthiazuron, monsiouron and noruron; Phenylurea herbicides such as anisuron, buturon, chlorbromuron, chloreturon, chlorotoluron, chlorlockon, dimuron, diphenoxuron, dimefuron, diuron, phenuron, fluoromethuron, fluorothiuron , Isoproturon, linuron, methiuron, methyldimron, methopenzuron, metobromuron, methoxuron, monolinuron, mononurone, neburon, paraflulon, phenobenjuron, siduron, tetrafluron And tidiazuron; Pyrimidinylsulfonylurea herbicides such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron, plazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halo Sulfuron, imazosulfuron, mesosulfuron, nicosulfuron, orthosulfamuron, oxasulfuron, primiumfuron, pyrazofurfuron, rimsulfuron, sulfomethuron, sulfosulfuron and tripleoxysulfuron; Triazinylsulfonylurea herbicides such as chlorsulfuron, cynosulfuron, etamethsulfuron, iodosulfuron, metsulfuron, prosulfuron, thifensulfuron, triasulfuron, tribenuron, triplelusulfuron and triglycerides Tosulfuron; Thiadiazolylurea herbicides such as butyuron, etidimuron, tebutiuuron, thiazafluron and tidiazuron; And unclassified herbicides such as acrolein, allyl alcohol, azaphenidine, benazolin, bentazone, benzobicycline, butidazole, calcium cyanamide, campbendichlor, chlorfenac, chlorfenprop, chlorflurazole, chlor Flurenol, caffeine, clomazone, CPMF, cresol, ortho-dichlorobenzene, dimepiperate, endortal, fluoromidine, flulidone, flulochloridone, flutarmone, fluthiacet, indanophan , Metazole, methyl isothiocyanate, nipyraclofen, OCH, oxadiargyl, oxadione, oxazilomepon, pentachlorophenol, pentoxazone, phenylmercury acetate, pinoxaden, prosulfolin, pyri Benzoxime, pyridphthalide, quinoclamin, rodetanyl, sulglycopene, tidiazimine, tridiphane, trimetaurone, tripropyndan and trytax.

Claims (10)

A compound of formula (I) <Formula I>

Where Het is represented by the formula

Represents; X is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ alkoxy , C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ⁶ where m is an integer from 0 to 2, COOR ⁴ or CONR ⁴ R ⁵ ; Y is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ¹ , wherein m is an integer from 0 to 2, COOR ⁴ , CONR ⁴ R ⁵ , aryl or heteroaryl; Z is C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ¹ (where m is an integer from 0 to 2), COOR ⁴ or CONR ⁴ R ⁵ ; n is an integer from 0 to 3; L represents a single bond, —CH ₂ — or —CH (CH ₂ ) _p −, where p is an integer from 1 to 3, wherein R ¹ , S and L or R ² , L and the co-carbon to which they are attached Together represent a 4, 5 or 6 membered ring having up to 1 heteroatom; R ¹ represents C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ haloalkenyl, arylalkyl, heteroarylalkyl Or together with L or R ² form a 4, 5 or 6 membered saturated ring; R ² and R ³ are independently hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloal Kenyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, CN, SO _m R ⁶ where m is an integer from 0 to 2, COOR ⁴ , CONR ⁴ R ⁵ , arylalkyl, heteroarylalkyl Or R ² and R ³ and the co-carbon to which they are attached form a 3 to 6 membered ring, or R ² and R ¹ together form a 4, 5 or 6 membered saturated ring; R ⁴ and R ⁵ are independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ haloalkenyl, Aryl, heteroaryl, arylalkyl or heteroarylalkyl; R ⁶ represents C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ haloalkenyl, arylalkyl, heteroarylalkyl Represent; Q represents NO ₂ or CN. The compound of claim 1, wherein Q represents CN. The compound of claim 1, wherein R ² and R ³ independently represent hydrogen or C ₁ -C ₄ alkyl, or R ₂ and R ₃ and the co-carbon to which they are attached form a 3 to 6 membered ring. The compound of claim 1, wherein Het represents the formula:

(Wherein Y is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ¹ , wherein m = 0-2, COOR ⁴ , CONR ⁴ R ⁵ , aryl or heteroaryl; Z is C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ haloalkenyl, C ₁ -C ₄ haloalkoxy, CN, NO ₂ , SO _m R ¹ , where m = 0 to 2, represents COOR ⁴ or CONR ⁴ R ⁵ The compound of claim 4, wherein Y represents hydrogen and Z represents C ₁ -C ₂ haloalkyl. The compound of claim 1 having the formula

(Wherein Het, Q, R ² and R ³ are as defined in claim 1) The compound of claim 1 having the formula

(Wherein p is an integer from 1 to 3, Het, Q, R ² and R ³ are as defined in claim 1) The compound of claim 1 having the formula

(Wherein p is an integer from 1 to 3, Het and Q are as defined in claim 1) A composition for controlling insects, comprising the compound of claim 1 in combination with a botany-acceptable carrier. A method of controlling insects, comprising applying the compound of claim 1 to an area where control is desired.